3 - acyloxy - 4 - halo - tetrahydrothiophene - 1,1 - dioxides and 3-acyloxy-2(h)-thiophene-1,1-dioxides



United States Patent 3,526,640 3 ACYLOXY 4 HALO TETRAHYDROTHIO- PHENE 1,1 DIOXIDES AND 3-ACYLOXY- 2(H)-THIOPHENE-1,1-DIOXIDES George G. King, Guilford, and Andrew J. Esposito, New Haven, Conn., assignors, by mesne assignments, to The Ansul Company, a corporation of Wisconsin No Drawing. Filed Apr. 16, 1968, Ser. No. 721,628 Int. Cl. A01n 9/14; C07d 63/04, 63/08 US. Cl. 260-3321 9 Claims ABSTRACT OF THE DISCLOSURE A series of 3-acyloxy-4-halo-tetrahydrothiophene-1,1- dioxides have the formula RCOUX and a series of 3-acy1oxy-2(H)-thiophene-1,1-dioxides having the formula 3 RJIO IT SJ 02 wherein X is halogen and R is aryloxyalkyl, haloaryloxyalkyl, loweralkyl substituted aryloxyalkyl, loweralkyl substituted haloaryloxyalkyl or nitroaryloxyalkyl are provided by reacting a 3-halo-4hydroxysu1folane With an ap propriate acyl halide. These compounds are particularly valuable as herbicides.

This invention relates to a series of 3-acyloxy-4-halotetrahydrothiophene-1,1-dioxides having the formla wherein X is halogen, i.e., fluorine, chlorine, bromine or iodine, and R is aryloxyalkyl, haloaryloxyalkyl, loweralkyl substituted aryloxyalkyl, loweralkyl substituted haloaryloxyalkyl or nitroaryloxyalkyl. This invention also relates to a series of 3-acyloxy-2(H)-thiophene-1,1- dioxides having the formula wherein R is a previously described.

Various substituted acyloxyhalotetrahydrothiophene-1, l-dioxides and acyloxy-Z (H)-thiophene-1,1-dioxides have been previously prepared and reported in the literature. Thus, N. J. Baker et al. in Rec. Trav. Chim., 61, 785 (1942) disclose the preparation of 3-acetyloxy-4-bromotetrahydrothiophene-l,l-dioxide while 3-benzoyloxy-4- chlorotetrahydrothiophene-1,l-dioxide is described in US. Pat. 2,460,233. The preparation of various acyloxy- 2(H)-thiophene-1,1-dioxides is discussed in US. Pat. 2,610,192 which discloses the compound 3-acetyloxy- 2 (H) -thiophene-l, l-dioxide.

, 3,526,640 Patented Sept. 1, 1970 scribed.

HO X

I i RCOCl I s 02 III phenoxypropionyl chloride, phenoxybutyryl chloride,

phenoxyvaleryl chloride, 2-chlorophenoxyacetyl chloride, 2,4 -dibromophenoxyacetyl chloride, 2-chloro-4-bromophenoxyacetyl chloride, 3-chlorophenoxyacetyl chloride, 4-chlorophenoxyacetyl chloride, 2,4-dichlorochlorophenoxyacetyl chloride, 3,4-dichlorophenoxyacetyl chloride, 2, 6-dichlorophenoxyacetyl chloride, 2,4,5-trichlorophenoxyacetyl chloride, 2-chlorophenoxybutyryl chloride, 2, 4-dichlorophenoxyvalery1 chloride, 2 methylphenoxyacetyl chloride, Z-n-butylphenoxyacetyl chloride, Z-methyl-4-isopropylphenoxyacetyl chloride, 4-t-butylphenoxyacetyl chloride, 4-ethylphenoxyacetyl chloride, 2,4-diisopropylphenoxyacetyl chloride, 2,4-dimethylphenoxyacetyl chloride, 2-methylphenoxypropionyl chloride, 2-methyl- 4-isopropylvaleryl chloride, p-nitrophenoxyacetyl chloride, 2,4,S-trinitrophenoxyacetyl chloride, 2-chloro-4- nitrophenoxyacetyl chloride and p-nitrophenoxybutyryl chloride.

While any acyl halide III can be suitably employed herein, preferred embodiments employ those compounds III wherein R is halophenoxy(lower)alkyl or loweralkyl substituted halophenoxyflower) alkyl.

The nature of the product obtained from the reaction of 3-halo-4-hydroxysulfolane with an acyl halide IH de pends on several variables, such as reaction temperature and the presence of a predetermined quantity of an acidbinding agent.

Thus, 3-acyloxy-4-halo-tetrahydrothiophene-1,1-dioxides I are obtained by carrying out the aforementioned reaction in the presence of an inert solvent at a temperature between about 10 and about C. Suitable inert solvents include aromatic solvents such as benzene, toluene, xylene, etc. The gaseous hydrogen halide by-product is readily evolved and removed from the reaction mixture by conventional means where elevated temperatures are employed.

The compounds 3-acyloxy-4-halo-tetrahydrothiopene- 1,1-dioxides I are also obtained by employing certain acid-binding agents in the above reaction in a quantity that is stoichiometric with respect to the acyl halide. Thus, the use of such materials as triethylamine and pyridine in the stipulated amounts Will provide compounds I while allowing the reaction to be carried out at lower temperatures within the aforementioned range. Preferably, inert solvents such as the previously described aromatics; ketones such as acetone, methyl ethyl ketone, etc. are employed.

The preparation of 3-acyloxy-2(H)-thiophene-1,1-dioxides II is carried out by utilizing one of the aforementioned acid-binding agents in an amount sufl'lcient to bind both the ring halogen and the halogen in the acyl halide. The same temperature ranges and inert solvents are preferably employed in this reaction. Other basic reagents such as sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, etc. can also be suitably employed as acid-binding agents.

Alternately, compounds I may be dehydrohalogenated to provide 3-acyloxy-2(H)-thiophene-1,1-dioxides II by reaction with an acid-binding agent as previously described.

Compounds I and II are readily obtained in high yield and excellent purity and are isolated from the reaction mixture by conventional means such as filtration, crystallization, etc.

The 3-acyloxy-4-halo-tetrahydrothiophene-1,1-dioxides I and 3-acyloxy-2(H)-thiophene-1,l-dioxides II are particularly valuable agricultural chemicals. Thus, they have exhibited strong herbicidal properties. Generally they are mixed with various adjuvants in these applications and low concentrations of the compounds are extremely effective.

For example, the compounds of this invention are excellent aquatic herbicides. Thus, when employed in an aqueous formulation containing 10 ppm. of the herbicide, 3-(2-chlorophenoxyacetoxy)-4-chlorotetrahydrothiophene- 1,1-dioxide and 3-(2,4-dichlorophenoxyacetoxy)-4-chlorotetrahydrothiophene 1,1 dioxide were 100% effective against duckweed.

The compounds I and II of this invention are also valuable post-emergence herbicides. For example, at a rate of application of 20 pounds per acre 3- (4-chloro-o-tolyloxyacetoxy) -4-chlorotetrahydrothiophene-1,1-dioxide,

3-( 2-chlorophenoxyacetoxy-4-bromotetrahydrothiophene- 1,1-dioxide and 3-( 2,4,5 -trichlorophenoxyacetoxy) -4-bromotetrahydrothiophene-1,1-dioxide were 100% effective against mustard and pigweed.

The pre-emergence herbicidal effectiveness of compounds I and II is illustrated by the control of crabgrass,

mustard and pigweed by at a rate of application of 20 pounds per acre.

The following examples are presented to illustrate the preparation of various 3-acyloxy-4-halo-tetrahydrothiophene-1,1-dioxides I and 3-acyloxy-2(H)-thiophene-1,ldioxides II in accordance with the practice of this invention.

EXAMPLE 1 o-Chlorophenoxyacetyl chloride (20.5 g., 0.1 mole) was added dropwise to a boiling acetone solution of 3-chloro- 4-hydroxysulfolane (16.8 g., 0.1 mole) and triethylamine (10 g., 0.1 mole). After completion of the addition, the reaction mixture was heated at reflux for 6 hours and allowed to cool to room temperature. Then the reaction mixture was poured onto ice, thereby providing a white precipitate which was recrystallized from ethanol to yield 12 g. of a white solid, M.P. 119-21" C. The following analytical data revealed that 3-(2-chlorophenoxyacetoxy)- 4-chlorotetrahydrothiophene-1,l-dioxide had been obtained.

Analysis.--Calcd. for C H Cl S (percent): C, 42.39; H, 3.79; Cl, 20.85. Found (percent): C, 42.15; H, 3.58; Cl, 21.05.

4 EXAMPLE 2 Following the procedure of Example 1, p-chlorophenoxyacetyl chloride (20.5 g., 0.1 mole) was reacted for 20 hours with 3-chloro-4-hydroxysulfolane (16.8 g., 0.1 mole) in the presence of pyridine (7.9 g., 0.1 mole) to provide 10 g. of a white solid, M.P. -6 C. The following analytical data revealed that 3-(4 chlorophenoxyacetoxy)-4-chlorotetrahydrothiophene-1,1-dioxide had been obtained.

Analysis.Calcd. for C H Cl O S (percent): C, 42.39; H, 3.79; Cl, 20.85. Found (percent): C, 42.58; H, 3.55; CI, 20.62.

EXAMPLE 3 Following the procedure of the previous examples, 2,4- dichlorophenoxyacetyl chloride (23.9 g. 0.1 mole) was reacted for 20 hours with 3-chloro-4-hydroxysulfolane (16.8 g., 0.1 mole) in the presence of pyridine (7.9 g., 0.1 mole) to provide 23 g. of a white solid, M.P. 22" C. The following analytical data revealed that 3-(2,4- dichlorophenoxyacetoxy) 4-chlorotetrahydrothiophene- 1,1-dioxide had been obtained.

Analysis.-Calcd. for C H Cl O S (percent): C, 38.57; H, 2.97; Cl, 28.46. Found (percent): C, 38.82; H, 2.97; Cl, 27.91

EXAMPLE 4 Following the procedure of the previous examples, 2,4, S-trichlorophenoxyacetyl chloride (27.4 g.,) 0.1 mole) was reacted for 6 hours with 3-chloro-4-hydroxysulfolane (16.8 g., 0.1 mole) in the presence of pyridine (7.9 g., 0.1 mole) to provide 12 g. of a white solid, M.P. 58 C. The following analytical data revealed that 3- chloro 4-(2,4,S-trichlorophenoxyacetoxy) tetrahydrothiophene-1,1-dioxide had been obtained.

Analysis.Calcd. for C H Cl O S (percent): C, 35.23; H, 2.46; CI, 34.66; S, 7.84. Found (percent): C, 35.44; H, 2.50; Cl, 34.43; S, 7.78.

EXAMPLE 5 Following the procedure of the previous examples, o-chlorophenoxyacetyl chloride (20.5 g., 0.1 mole) was reacted for 6 hours with 3-bromo-4-hydroxysulfolane (19.7 g., 0.1 mole) in the presence of triethylamine (10 g., 0.1 mole) to provide 10 g. of a white solid, M.P. 142- 3 C. The following analytical data revealed that 3-(2- chlorophenoxyacetoxy) 4 bromotetrahydrothiophene- 1,1-dioxide had been obtained.

Analysis.Calcd. for C H BrClO S (percent): C, 37.39; H, 3.35; Cl, 9.19. Found (percent): C, 37.64; H, 3.48; Cl, 9.01.

EXAMPLE 7 Following the procedure of the previous examples, 2,4,S-trichlorophenoxyacetyl chloride (27.4 g., 0.1 mole) was reacted for 20 hours with 3-bromo-4-hydroxysulfolane (19.7 g., 0.1 mole) in the presence of pyridine (7.9 g., 0.1 mole) to provide 23 g. of a white solid, M.P. 85-7 C. The following analytical data revealed that 3- (2,4,5-trichlorophenoxyacetoxy) 4 brornotetrahydrothiophene-1,1-dioxide had been obtained.

Analysis.-Calcd. for C H BrCl O S (percent): C, 31.85; H, 2.23; CI, 23.50. Found (percent): C, 31.63; H, 2.26; Cl, 23.18.

EXAMPLE 8 Following the procedure of the previous examples, 4- chloro-2 methylphenoxyacetyl chloride (21.9 g., 0.1 mole) was reacted for 6 hours with 3-bromo-4-hydroxysulfolane (19.7 g., 0.1 mole) in the presence of pyridine (7.9 g., 0.1 mole) to provide 7 g. of 3-(4-chloro-o-tolyloxyacetoxy) 4 bromotetrahydrothiophene-1,1-dioxide, M.P. 868 C.

EXAMPLE 9 Following the procedure of the previous examples, o-chlorophenoxyacetyl chloride (20.5 g., 0.1 mole) was reacted for 19 hours with 3-bromo-4-hydroxysulfolane (19.7 g., 0.1 mole) in the presence of triethylamine (20.2 g., 0.2 mole) to provide 15 g. of a White solid, M.P. 142 4 C. The following analytical data revealed that 3- (2-chlorophenoxyacetoxy) 2(H)-thiophene-1,1-dioxide had been obtained.

Analysis.-Calcd. for C H ClO S (percent): C, 47.61; H, 3.66; CI, 11.71. Found (percent): C, 47.27; H, 3.49; CI, 11.88.

EXAMPLE Following the procedure of the previous examples, 4- chlorophenoxyacetyl chloride (20.5 g., 0.1 mole) was reacted for hours with 3 bromo-4-hydroxysulfolane (19.7 g., 0.1 mole) in the presence of triethylamine (20.2 g., 0.2 mole) to provide 18 g. of a white solid, M.P. 14l3 C. The following analytical data revealed that 3-(4-chlorophenoxyacetoxy) 2(H)-thiophene 1,1- dioxide had been obtained.

Analysis.Calcd. for C H ClO S (percent): C, 47.61; H, 3.66; Cl, 11.71. Found (percent): C, 47.85; H, 3.63; Cl, 11.92.

EXAMPLE 11 Following the procedure of the previous examples, 2,4- dichlorophenoxyacetyl chloride (23.9 g., 0.1 mole) was reacted for 19 hours with 3-brorno-4-hydroxysulfolane (19.7 g., 0.1 mole) in the presence of triethylamine (20.2 g., 0.2 mole) to provide 20 g. of a white solid, M.P. 165-7 C. The following analytical data revealed that 3-(2,4 dichlorophenoxyacetoxy) 2(H)-thiophene- 1,1-dioxide had been obtained.

Analysis.-Calcd. for C H Cl O S (percent): C, 42.75; H, 2.99; CI, 21.03. Found (percent): C, 42.58; H, 2.80; Cl, 21.14.

EXAMPLE 12 Following the procedure of the previous examples, 2,4,5-trichlorophenoxyacetyl chloride (27.4 g., 0.1 mole) was reacted for 20 hours with 3-bromo-4-hydroxysulfolane (19.7 g., 0.1 mole) in the presence of triethylamine (20.2 g., 0.2 mole) to provide 7 g. of a white solid, M.P. 168-70 C. The following analytical data revealed that 3-(2,4,5-trichlorophenoxyacetoxy) 2(H)-thiophene- 1,1-dioxide had been obtained.

Analysis.Calcd. for C H Cl O S (percent): C, 38.78; H, 2.44; Cl, 28.61;Found (percent) C, 39.11; H, 2.32; CI, 27.92, 27.77.

EXAMPLE 13 Following the procedure of the previous examples, 4- chloro-2-methylphenoxyacetyl chloride (21.9 g., 0.1 mole) was reacted for 4 hours with 3-bromo-4-hydroxysultolane (19.7 g., 0.1 mole) in the presence of triethylamine (20.2 g., 0.2 mole) to provide 13 g. of a white solid, M.P. 99-101 C. The following analytical data re- 6 vealed that 3-(4-chl0ro-o-tolyloxyacetoxy) 2(H)-thiohene-Ll-dioxide had been obtained.

Analysis.Calcd. for C H ClO S (percent): C, 49.32; H, 4.08; Cl, 11.20. Found (percent) C, 49.53; H, 4.14; Cl, 11.20.

What is claimed is:

1. A compound selected from the group consisting of (a) 3-acyloxy-4-halo-tetrahydrothiophene-1,1 dioxides having the formula u RCO TX i and (b) 3-acyloxy-2(H)-thiophene-l,1-dioxides having the formula wherein X is halogen and R is phenoxy(lower)alkyl, halophenoxy(lower)alkyl, loweralkyl substituted phenoxy(lower)alkyl, loweralkyl substituted halophenoxy(lower)alkyl or nitrophenoxyflower)alkyl.

2. The 3-acyloxy-4-halo-tetrahydrothiophene 1,1 dioxide of claim 1 wherein X is halogen and R is halophenoxy(lower)alkyl or loweralkyl substituted halophenoxy (lower) alkyl.

3. The 3-acyloxy-4-ha1o-tetrahydrothiophene 1,1 di- F oxide of claim 2 having the name 3-(2,4,5-trichlorophenoxyacetoxy) 4 bromotetrahydrothiophene 1,1-dioxide.

4. The 3-acyloxy-4-halo-tetrahydrothiophene 1,1-dioxide of claim 2 having the name 3-(2-chlorophenoxyacetoxy) -4-bromo-tetrahydrothiophenel l-dioxide.

5,. The 3-acyloxy-4-halo-tetrahydrothiophene 1,1 dioxide of claim 2 having the name 3-(4-chloro-o-tolyloxyacetoxy) -4-chlorotetrahydrothiophenc-1,l-dioxide.

6. The 3-acyloxy-2(H)-thiophene-1,1-dioxide of claim 1 wherein X is halogen and R is halophenoxy(lower) alkyl or loweralkyl substituted halophenoxy(lower) alkyl.

7. The 3-acyloxy-2(H)-thiophene-1,l-dioxide of claim 6 having the name 3(2-chlorophenoxyacetoxy) 2(H)- thiophene-1,1-di0xide.

8. The 3-acyloxy-2(H)-thiophene-1,1-dioxide of claim 6 having the name 3-(2,4-dichlorophenoxyacetoxy)-2(H)- thiophene- 1 l-dioxide.

9. The 3-acyloxy-2(H)-thiophene-1,1-dioxide of claim 6 having the name 3-(4-chloro-o-tolyloxyacetoxy)-2-(H)- 0 thiophene-1,1-dioxide.

References Cited UNITED STATES PATENTS 2,460,233 1/ 1949 Morris et al 260-829 HENRY R. JILES, Primary Examiner C. M. SHURKO, Assistant Examiner US. Cl. X.R. 

